CN101796008A - Processes for making dialkyl ethers from alcohols - Google Patents

Processes for making dialkyl ethers from alcohols Download PDF

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CN101796008A
CN101796008A CN200880105308A CN200880105308A CN101796008A CN 101796008 A CN101796008 A CN 101796008A CN 200880105308 A CN200880105308 A CN 200880105308A CN 200880105308 A CN200880105308 A CN 200880105308A CN 101796008 A CN101796008 A CN 101796008A
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acid
reaction mixture
ionic liquid
dialkyl ether
alcohol
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M·A·哈梅
M·B·德亚莫雷
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups

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Abstract

Processes for preparing dialkyl ethers from C4 to C8 straight-chain alcohols using an ionic liquid.

Description

Be used for preparing the method for dialkyl ether by alcohol
Present patent application requires the right of priority and the power of being benefited of the U.S. Provisional Application 60/970,099 submitted on September 5th, 2007, described provisional application with way of reference incorporate in full this paper as its part to be used for all purposes.
Technical field
The present invention relates to prepare the method for dialkyl ether by straight chain alcohol.
Background of invention
Ether such as dibutyl ether can be used as solvent and diesel cetane-number toughener." Ahead of the Curve " (Ethanol Producer Magazine, in November, 2005) and WO 01/18154 referring to for example Kotrba wherein disclose the diesel oil formulation examples that comprises dibutyl ether.
Preparing the method for ether by alcohol, is known such as the method that is prepared dibutyl ether by butanols, and is summarized in people's such as Kara the 5th edition the 10th volume of Kirk-Othmer Encyclopedia of Chemical Technology the 5.3rd chapter 567-583 page or leaf.Described reaction is generally by carrying out dehydration of alcohols with sulfuric acid, or by at high temperature, catalytic dehydration carries out on iron(ic) chloride, copper sulfate, silicon-dioxide or siallite.People such as Bringue [J.Catalysis (2006) 244:33-42] disclose the thermostability ion exchange resin as 1-amylalcohol to two n-pentyl ether dehydration reaction catalyzer.WO 07/38360 discloses the method for preparing polytrimethylene ether glycol in the presence of ionic liquid.
Yet what still need to have commercial advantage prepares the method for ether by alcohol.
Summary of the invention
Invention disclosed herein comprise by alcohol prepare dialkyl ether method, this method purposes and by this method that obtain with obtainable product.
This paper has described the feature of some method of the present invention in the context of one or more specific embodiments, described embodiment combines various these category features.Yet scope of the present invention is not limited to the description of independent certain the several feature in any specific embodiments, and the present invention comprises that also (1) is less than time combination of all features of any described embodiment, and described time combined feature is not exist formation time combination institute elliptical feature; (2) each feature is included in the combination of any described embodiment independently; (3) can only the selected feature in two or more described embodiments be sorted out and other combination of features of formation with disclosed other features in its elsewhere of this paper by optional.Some specific embodiments in this paper method are as follows:
In method disclosed herein, in reaction mixture, prepare dialkyl ether, preparation method is as follows: (a) at least a ion liquid in the presence of, make at least a C 4-C 8Straight chain alcohol contacts with at least a homogeneous acid catalyst, forming the dialkyl ether phase that (i) comprises the reaction mixture of dialkyl ether, with the ionic liquid of (ii) reaction mixture mutually; And (b) dialkyl ether of reaction mixture is separated mutually from the ionic liquid of reaction mixture, to reclaim the dialkyl ether product; Wherein ionic liquid is represented by the following formula structure:
Figure GPA00001039864800021
Wherein:
In positively charged ion, Z is-(CH 2) n-, wherein n is 2 to 12 integer; And R 2, R 3And R 4Be selected from independently of one another H ,-CH 3,-CH 2CH 3, and C 3-C 6The straight or branched univalent alkyl; And
A -Be negatively charged ion, this negatively charged ion is selected from [CH 3OSO 3] -, [C 2H 5OSO 3] -, [CF 3SO 3] -, [HCF 2CF 2SO 3] -, [CF 3HFCCF 2SO 3] -, [HCClFCF 2SO 3] -, [(CF 3SO 2) 2N] -, [(CF 3CF 2SO 2) 2N] -, [CF 3OCFHCF 2SO 3] -, [CF 3CF 2OCFHCF 2SO 3] -, [CF 3CFHOCF 2CF 2SO 3] -, [CF 2HCF 2OCF 2CF 2SO 3] -, [CF 2ICF 2OCF 2CF 2SO 3] -, [CF 3CF 2OCF 2CF 2SO 3] -, [(CF 2HCF 2SO 2) 2N] -, and [(CF 3CFHCF 2SO 2) 2N] -
Ether such as dialkyl ether by the preparation of this paper method can be used as solvent, softening agent, and can be used as the additive in transport fuel such as gasoline, diesel oil and the rocket engine fuel.
Detailed Description Of The Invention
Herein disclosed is the method that in the presence of at least a ionic liquid and at least a acid catalyst, prepares dialkyl ether.When using homogeneous acid catalyst, these methods provide advantage in the following areas: the product dialkyl ether can separate mutually and obtains recovery from the ionic liquid that comprises ionic liquid and acid catalyst with product phase form.
In the description of this paper method,, provide following definition structure for some term that is adopted in the specification sheets different piece:
" alkane " or " alkane compound " is for having general formula C nH 2n+2Stable hydrocarbon, and can be straight chain, side chain or ring compound.
" alkene " or " olefin(e) compound " for to comprise the unsaturated hydrocarbons of one or more carbon-to-carbon double bonds, and can be straight chain, side chain or ring compound.
" alkoxyl group " is the straight or branched alkyl via the Sauerstoffatom bonding.
" alkyl " is for by removing a hydrogen atom by alkane deutero-univalent perssad :-C from any carbon atom nH 2n+1, n=1 wherein.Alkyl can be C 1-C 20Straight chain, side chain or cyclic alkyl.The example of suitable alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, tri-methyl-amyl and ring octyl group.
" aromatic hydrocarbons " or " aromatic hydroxy compound " comprises benzene and the compound of similar benzene aspect chemical conduct.
" aryl " is the univalent perssad of aromatic ring carbon atom for its free valency.Described aryl moiety can comprise one or more aromatic rings, and can be replaced by inertia group, and described inertia group is that it exists the group that does not influence reaction.The example of suitable aryl comprises phenyl, aminomethyl phenyl, ethylphenyl, n-propyl phenyl, n-butylphenyl, tert-butyl-phenyl, xenyl, naphthyl and ethyl naphthyl.
The alkoxyl group that " fluoroalkyl " replaced by fluorine atom at least one hydrogen atom wherein.
The alkyl that " fluoro-alkyl " replaced by fluorine atom at least one hydrogen atom wherein.
" halogen " is bromine, iodine, chlorine or fluorine atom.
" assorted alkyl " is for having one or more heteroatomic alkyl.
" heteroaryl " is for having one or more heteroatomic aryl.
" heteroatoms " is not to be the atom of carbon in the unit structure.
When relating to alkane, alkene, alkoxyl group, alkyl, aryl, fluoroalkyl, fluoro-alkyl, assorted alkyl, heteroaryl, perfluoro alkoxy or perfluoroalkyl or part, " optional replaced by at least one unit, described unit is selected from " is meant that the one or more hydrogen on the carbochain of described group or part can be replaced by one or more described substituting groups unit independently.For example, choose substituted-C wantonly 2H 5Group or part can be and be not limited to-CF 2CF 3,-CH 2CH 2OH or-CF 2CF 2I, wherein substituting group is made up of F, I and OH.
The alkoxyl group that " perfluoro alkoxy " all replaced by fluorine atom for all hydrogen atoms wherein.
The alkyl that " perfluoroalkyl " all replaced by fluorine atom for all hydrogen atoms wherein.
In method disclosed herein, in reaction mixture, prepare dialkyl ether, preparation method is as follows: (a) make at least a C at least a in the presence of ion liquid 4-C 8Straight chain alcohol and the contact of at least a homogeneous acid catalyst with form (i) comprise dialkyl ether reaction mixture dialkyl ether mutually, with the ionic liquid of (ii) reaction mixture mutually; And (b) dialkyl ether of reaction mixture is separated mutually from the ionic liquid of reaction mixture, to reclaim the dialkyl ether product; Wherein ionic liquid is represented by the following formula structure:
Wherein:
In positively charged ion, Z is-(CH 2) n-, wherein n is 2 to 12 integer; And R 2, R 3And R 4Be selected from independently of one another H ,-CH 3,-CH 2CH 3, and C 3-C 6The straight or branched univalent alkyl; And
A -Be negatively charged ion, this negatively charged ion is selected from [CH 3OSO 3] -, [C 2H 5OSO 3] -, [CF 3SO 3] -, [HCF 2CF 2SO 3] -, [CF 3HFCCF 2SO 3] -, [HCClFCF 2SO 3] -, [(CF 3SO 2) 2N] -, [(CF 3CF 2SO 2) 2N] -, [CF 3OCFHCF 2SO 3] -, [CF 3CF 2OCFHCF 2SO 3] -, [CF 3CFHOCF 2CF 2SO 3] -, [CF 2HCF 2OCF 2CF 2SO 3] -, [CF 2ICF 2OCF 2CF 2SO 3] -, [CF 3CF 2OCF 2CF 2SO 3] -, [(CF 2HCF 2SO 2) 2N] -, and [(CF 3CFHCF 2SO 2) 2N] -
The suitable alcohol that can be used for the preparation dialkyl ether of this paper comprises straight chain alcohol for example propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol and n-Octanol.Therefore dialkyl ether by the preparation of the method for this paper can be two positive alkyl oxides, but it also can be following ether, and wherein one or two carbochain on it is derived from C 4-C 8The identical or different isomer of straight chain alcohol.For example, be used as at propyl carbinol under the situation of alcohol reactant, one or two butyl part of dialkyl ether product can be 1-butyl, 2-butyl, the tertiary butyl or isobutyl-independently.
Ionic liquid is to be the organic compound of liquid down in room temperature (about 25 ℃).They are different from most salt, because they have low-down fusing point, they tend to be liquid in wide temperature range, and have shown to have high thermal capacitance.Ionic liquid is gone up does not substantially have vapour pressure, and they can be neutral, acid or alkaline.According to positively charged ion and anionic characteristic, ion liquid characteristic will demonstrate some variation.Yet can be used for that ion liquid positively charged ion of the present invention or negatively charged ion go up substantially can be any positively charged ion or negatively charged ion, makes positively charged ion and negatively charged ion lump together to be formed on that being equal to or less than about 100 ℃ is fluidic organic salt down.
According to positively charged ion and/or anionic characteristic, ion liquid physics and chemical property will demonstrate some variation.For example, increase the chain length of the one or more alkyl chains of positively charged ion, will influence the ionic liquid characteristic, such as fusing point, hydrophilic/lipophilic, density and solvation intensity.Anionic selection can influence for example fusing point, water solubility and acidity and the coordination characteristic of described composition.Positively charged ion and anionic selection to the influence of ionic liquid physics and chemical property by Wasserscheid and Keim[Angew.Chem.Int.Ed. (2000) 39:3772-3789] and Sheldon[Chem.Commun. (2001) 2399-2407] summarize.
Be applicable to that the ionic liquid in this paper method can be synthetic by general method: in the presence of catalyzer and hydrogen, levulinic acid or its ester are contacted with diamines, to form N-alkyl pyrrolidin-2-one.By the acyclic nitrogen of described pyrrolidin-2-one is quaternized, described pyrrolidin-2-one is changed into suitable ionic liquid then.These ionic liquids based on pyrrolidone are green ionic liquids, and they can be by the renewable biomass feed preparation of cheapness.These class methods are discussed further in U.S. Patent Publication 7,157, in 588, described patent disclosure with way of reference incorporate in full this paper as its part to be used for all purposes.
With respect to C contained in the reaction mixture 4-C 8The weight of alcohol, the content of ionic liquid in reaction mixture can be about 0.1% or bigger by weight, or about 2% or bigger, but be about 25% or lower, or about 20% or lower.
Be applicable to that the catalyzer in this paper method reaches the speed of molecular balance from nonexpendable basically material in reaction for increase.In preferred embodiments, described catalyzer is a homogeneous catalyst, and in this sense, described catalyzer is present in the uniform homophase mutually with reactant, and described catalyzer and reactant by molecular level be scattered in this mutually in.
In one embodiment, to be suitable for the acid make this paper homogeneous catalyst be pKa less than about 4 those; In another embodiment, to be suitable for the acid make this paper homogeneous catalyst be pKa less than about 2 those.
In one embodiment, the homogeneous acid catalyst that is applicable to this paper can be selected from mineral acid, organic sulfonic acid, heteropolyacid, fluoro-alkyl sulfonic acid, metal sulfonate, metal trifluoroacetate acetate, their mixture and their combination.In another embodiment, described homogeneous acid catalyst is optional from sulfuric acid, fluosulfonic acid, phosphorous acid, tosic acid, Phenylsulfonic acid, phospho-wolframic acid, phospho-molybdic acid, trifluoromethanesulfonic acid, nine fluorine fourth sulfonic acid, 1,1,2,2-tetrafluoro ethyl sulfonic acid, 1,1,2,3,3,3-hexafluoropropanesulacidc acidc, Bismuth triflate, trifluoromethanesulfonic acid yttrium, Ytterbiumtriflate, trifluoromethanesulfonic acid neodymium, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid scandium and trifluoromethanesulfonic acid zirconium.
With respect to C contained in the reaction mixture 4-C 8The content of alcohol, the content of catalyzer in reaction mixture is about 0.1% or bigger by weight, or about 1% or bigger, but be about 20% or lower, or about 10% or lower, or about 5% or lower.
Described reaction can be carried out to about 300 ℃ temperature at about 50 ℃.In one embodiment, described temperature is about 100 ℃ to about 250 ℃.Described reaction can be carried out to the pressure of about 20.7MPa at about normal atmosphere (about 0.1MPa).In a more particular embodiment, described pressure is that about 0.1MPa is to about 3.45MPa.Described reaction can be carried out under inert atmosphere, and rare gas element is to be suitable for as nitrogen, argon gas and helium.
In one embodiment, described being reflected in the liquid phase carried out.In alternative embodiment, described being reflected under high temperature and/or the high pressure carried out, and makes the product dialkyl ether be present in the vapor phase.By reducing temperature and/or pressure, can make such vapor phase dialkyl ether be condensed into liquid.The reduction of temperature and/or pressure can occur in the reaction vessel self, or alternatively, described vapor phase can be collected in the independent container, therein described vapor phase is condensed into liquid phase then.
Reaction times will be depended on many factors, such as reactant, reaction conditions and reactor, and can be conditioned to obtain the dialkyl ether of high yield.Described reaction can become batch mode or continuous mode to carry out.
In this reaction, use ion liquid advantage to be: because the generation of dialkyl ether product, the dialkyl ether product is retained in first phase (" dialkyl ether phase ") of reaction mixture, described first with wherein keep ionic liquid and catalyzer second mutually (" ionic liquid phase ") be isolating.Therefore, can be easy to by decantation for example from acid catalyst (ionic liquid mutually) in reclaim one or more dialkyl ether products (dialkyl ether mutually in).
In another embodiment, the recirculation of isolated ionic liquid phase can be joined in the reaction mixture once more.One or more positive alcohol change into one or more dialkyl ethers and cause forming water.Therefore, when expectation will be contained in the ionic liquid recirculation of ionic liquid in mutually, may need ionic liquid is handled mutually to remove water.A kind of common treatment process that is used to remove water is to adopt distillation.Ionic liquid has negligible vapour pressure, and can be used for catalyzer of the present invention and generally have the boiling point higher than the boiling point of water; Therefore, distill described ionic liquid so that water is shifted out from the distillation tower top, and ionic liquid and catalyzer will shift out, and generally are possible from described tower bottom.The distillating method that is suitable for separation water outlet from ionic liquid is discussed further in the 7th edition (McGraw-Hill, 1997) the 13rd chapter " Distillation " of Chemical Engineers ' Handbook of Perry.(McGraw-Hill，1997)。In subsequent step, can maybe relict catalyst can be turned back in the reaction mixture with ionic liquid by filtering or the centrifugal relict catalyst of from ionic liquid, isolating.
Can be further purified and the former state use but the dialkyl ether of isolating and/or reclaiming is optional mutually.
In various other embodiments of the present invention, by selecting any independent positively charged ion described herein or disclosed and ionic liquid, can be used for preparing in the reaction mixture dialkyl ether by selecting any independent negatively charged ion described herein or disclosed to form.Correspondingly, in other embodiments, the ionic liquid subgroup of following formation can be used for reaction mixture and prepare dialkyl ether: (i) from the total group of positively charged ion described herein or disclosed, the positively charged ion subgroup of any scale of taking out with the various various combination forms of all of total group of single cells, (ii) from the total group of negatively charged ion described herein or disclosed, the negatively charged ion subgroup of any scale of taking out with all various various combination forms of total group of single cells.When forming ionic liquid or ionic liquid subgroup by the selection of carrying out as mentioned above, ionic liquid or ionic liquid subgroup can be used for there not being described member is under the situation of the positively charged ion that is excluded of total group of selecting from it and/or negatively charged ion group members, if and expectation, the member of total group members that can be excluded when using rather than this group of being comprised when using carries out described selection.
Each chemical formula shown in this article has been described all different independent compounds, described compound can be formed by following manner: (1) selects in variable group, substituting group or the numerical coefficient in stated limit, and every other variable group, substituting group or numerical coefficient remain unchanged, (2) in stated limit, then in other variable groups, substituting group or the numerical coefficient each is carried out same selection, and other remain unchanged.Except the selection of in the stated limit of any variable group, substituting group or numerical coefficient, being done by only a member of described group of this scope, a plurality of compounds can also by select in whole group group, substituting group or the numerical coefficient more than one but be less than all members and describe.When the selection of being done in the stated limit of any variable group, substituting group or numerical coefficient is to comprise (i) by the described whole group only a member of this scope, more than one of perhaps (ii) whole group but when being less than all members' child group, selected member not selectedly in whole group selects with those members that form the son group by neglecting.In the case, described compound or a plurality of compound can one or more variable groups, substituting group or numerical coefficient are defined as feature, it relates to variable whole group of stated limit, but the member who is left in the basket when wherein forming the son group is not in whole group.
Can obtain the mode of advantageous feature and effect with a series of foresight embodiment as described below (embodiment 1 to 2) formal description by this paper method.As these embodiment bases, the embodiment of these methods only is representational, and select those embodiments to come example the present invention not represent that condition, arrangement, method, scheme, reactant, technology or the rules do not described in these embodiments just are not suitable for these methods of enforcement, do not represent that perhaps the theme of not describing in these embodiments just is excluded outside the category of claims and equivalent thereof.
General material and method
Use following abbreviation:
Nucleus magnetic resonance is abbreviated as NMR; Vapor-phase chromatography is abbreviated as GC; The gaschromatographic mass spectrometry method is abbreviated as GC-MS; Tlc is abbreviated as TLC; Thermogravimetric analysis (uses Universal V3.9A TAinstrument analyser (TA Instruments, Inc., Newcastle, DE)) to be abbreviated as TGA.Degree centigrade be abbreviated as C, megapascal (MPa) is abbreviated as MPa, and gram is abbreviated as g, and kilogram is abbreviated as Kg, and milliliter is abbreviated as mL, hour is abbreviated as hr or h; Weight percent is abbreviated as weight %; Milliequivalent is abbreviated as meq; Fusing point is abbreviated as Mp; Dsc is abbreviated as DSC.
Chlorination 1-butyl-2,3-methylimidazole, chlorination 1-hexyl-3-Methylimidazole, chlorination 1-dodecyl-3-Methylimidazole, chlorination 1-hexadecyl-3-Methylimidazole, chlorination 1-octadecyl-3-Methylimidazole, imidazoles, tetrahydrofuran (THF), iodopropane, acetonitrile, perfluoro-hexyl iodide alkane, toluene, 1-butanols, oleum (20%SO 3), S-WAT (Na 2SO 3, 98%) and acetone derive from Acros (Hampton, NH).Potassium pyrosulfite (K 2S 2O 5, 99%) derive from MallinckrodtLaboratory Chemicals (Phillipsburg, NJ).Hydration potassium sulfite (KHSO 3xH 2O, 95%) sodium bisulfite (NaHSO, 3), yellow soda ash, sal epsom, phospho-wolframic acid, ether, 1,1,1,2,2,3,3,4,4,5,5,6,6-13 fluoro-8-iodo-octanes, tri octyl phosphine and chlorination 1-ethyl-3-Methylimidazole (98%) derive from Aldrich (St.Louis, MO).Sulfuric acid and methylene dichloride derive from EMD Chemicals, and Inc. (Gibbstown, NJ).Perfluor (ethyl vinyl ether), perfluor (methylvinylether), R 1216 and tetrafluoroethylene derive from DuPontFluoroproducts (Wilmington, DE).Chlorination 1-butyl methyl imidazoles derive from Fluka (Sigma-Aldrich, St.Louis, MO).Four normal-butyl bromination Phosphonium and tetradecyl (three n-hexyls) phosphonium chloride derive from Cytec (Canada Inc., Niagara Falls, Ontario, Canada).1,1,2,2-tetrafluoro-2-(five fluorine oxyethyl groups) sulfonate derives from SynQuestLaboratories, and Inc. (Alachua, FL).
Anionic preparation
(A) synthesize 1,1,2,2-tetrafluoro ethyl sulfonic acid potassium (TFES-K) ([HCF 2 CF 2 SO 3 ] - ):
To 1 gallon
Figure GPA00001039864800091
Add in the C276 reaction vessel hydration potassium sulfite (176g, 1.0mol), potassium pyrosulfite (610g, 2.8mol) and the solution of deionized water (2000mL).The pH of this solution is 5.8.Container is cooled to 18 ℃, empties to 0.10MPa, and use nitrogen purging.Emptying/purging circulation is repeated twice again.(TFE 66g), and is heated to 100 ℃, presses in this moment to be 1.14MPa to add tetrafluoroethylene then in described container.Temperature of reaction is risen to 125 ℃, and under this temperature, keep 3hr.When TFE pressure owing to reaction when descending, (each 20 to 30g) adds more TFE with the small-scale aliquots containig, with working pressure is roughly remained between 1.14 and 1.48MPa between.When having added 500g (5.0mol) TFE behind the initial preload 66g,, and be cooled to 25 ℃ with the container exhaust.The pH of transparent light yellow reaction soln is 10-11.By adding potassium pyrosulfite (16g), this solution is buffered to pH 7.
Vacuum removes water on rotatory evaporator, obtains wet solid.Then with solid at freeze dryer (Virtis Freezemobile 35x1; Gardiner, NY) the middle 72hr that places is to reduce to water-content about 1.5 weight % (1387g coarse fodder).The Theoretical Mass of all solids is 1351g.Mass balance is very near theoretical value, and isolated solid is owing to moisture has high slightly quality.The advantage that the lyophilize step of this adding has is to produce free-pouring white powder, in vacuum oven, handle and then obtain soap shape solid mass, described solid mass is very difficult to take out, and has to make it to break and with fragmentation it is taken out from flask.
By with reagent grade acetone extraction, filtration and dry, rough TFES-K further can be purified and separate.
19F?NMR(D 2O)δ-122.0(dt，J FH＝6Hz，J FF＝6Hz，2F)；-136.1(dt，J FH＝53Hz，2F)。
1H?NMR(D 2O)δ6.4(tt，J FH＝53Hz，J FH＝6Hz，1H)。
Water per-cent by the Karl-Fisher titration measuring: 580ppm.
C 4HO 2F 3The ultimate analysis calculated value of SK: C, 10.9:H, 0.5:N, 0.0 experimental result: C, 11.1:H, 0.7:N, 0.2.
Mp(DSC)：242℃。
TGA (air): under 367 ℃, 10 weight % loss; Under 375 ℃, 50 weight % loss.
TGA (N 2): under 363 ℃, 10 weight % loss; Under 375 ℃, 50 weight % loss.
(B) synthesize 1,1,2-three fluoro-2-(perfluor oxyethyl group) ethyl sulfonic acid potassium (TPES-K):
To 1 gallon
Figure GPA00001039864800101
Add in the C276 reaction vessel hydration potassium sulfite (88g, 0.56mol), potassium pyrosulfite (340g, 1.53mol) and the solution of deionized water (2000mL).Container is cooled to 7 ℃, empties to 0.05MPa, and use nitrogen purging.Emptying/purging circulation is repeated twice again.(PEVE, 600g 2.78mol), are heated to 125 ℃ then, and this moment, internal pressure was 2.31MPa to add perfluor (ethyl vinyl ether) then in this container.With temperature of reaction remain on 125 ℃ 10 hours.Pressure drops to 0.26MPa, and this moment is with container emptying and be cooled to 25 ℃.Crude reaction product is the white crystals throw out, and colourless waterbearing stratum (pH=7) is arranged on it.
This white solid 19It is pure desired product that F NMR spectrum shows, but and the spectrum in waterbearing stratum shows the impurity of fluoridizing of small but detection limit.Desired isomer is less dissolving in water, so it is with the pure form precipitation of isomery.
By the sintered glass funnel suction filtration, (60 ℃, 0.01MPa) middle drying is 48 hours at vacuum oven with wet filter cake then with the product slurries.Obtain canescence crystalline product (904g, 97% yield).
19F?NMR(D 2O)δ-86.5(s，3F)；-89.2，-91.3
(subsplit?ABq，J FF＝147Hz，2F)；-119.3，-121.2
(subsplit?ABq，J FF＝258Hz，2F)；-144.3
(dm，J FH＝53Hz，1F)。
1H?NMR(D 2O)δ6.7(dm，J FH＝53Hz，1H)。
Mp(DSC)263℃。
C 4HO 4F 8The ultimate analysis calculated value of SK: C, 14.3:H, 0.3.Experimental result: C, 14.1:H, 0.3.
TGA (air): under 359 ℃, 10 weight % loss; Under 367 ℃, 50 weight % loss.
TGA (N 2): under 362 ℃, 10 weight % loss; Under 374 ℃, 50 weight % loss.
(C) synthesize 1,1,2-three fluoro-2-(trifluoromethoxy) ethyl sulfonic acid potassium (TTES-K):
To 1 gallon
Figure GPA00001039864800111
Add in the C276 reaction vessel hydration potassium sulfite (114g, 0.72mol), potassium pyrosulfite (440g, 1.98mol) and the solution of deionized water (2000mL).The pH of this solution is 5.8.Container is cooled to-35 ℃, empties to 0.08MPa, and use nitrogen purging.Emptying/purging circulation is repeated twice again.(PMVE, 600g 3.61mol), are heated to 125 ℃ then, and this moment, internal pressure was 3.29MPa to add perfluor (methylvinylether) then in this container.With temperature of reaction remain on 125 ℃ 6 hours.Pressure drops to 0.27MPa, and this moment is with container emptying and be cooled to 25 ℃.After the cooling, forming the white crystals throw out of required product, is colourless clear aqueous solution (pH=7) above it.
This white solid 19It is pure desired product that F NMR spectrum shows, but and the spectrum in waterbearing stratum shows the impurity of fluoridizing of small but detection limit.Described solution is passed through sintered glass funnel suction strainer 6hr, to remove most water.Under 0.01MPa and 50 ℃, the dry 48hr of biscuit will wet then.Obtain 854g (83% yield) white powder like this.Because unwanted isomer is retained in the water during filtering, thus final product be isomery pure (by 19F and 1H NMR confirms).
19F?NMR(D 2O)δ-59.9(d，J FH＝4Hz，3F)；-119.6，-120.2(subsplit?ABq，J＝260Hz，2F)；-144.9
(dm，J FH＝53Hz，1F)。
1H?NMR(D 2O)δ6.6(dm，J FH＝53Hz，1H)。
Water per-cent by the Karl-Fisher titration measuring: 71ppm.
C 3HF 6SO 4The ultimate analysis calculated value of K: C, 12.6:H, 0.4:N, 0.0 experimental result: C, 12.6:H, 0.0:N, 0.1.
Mp(DSC)257℃。
TGA (air): under 343 ℃, 10 weight % loss; Under 358 ℃, 50 weight % loss.
TGA (N 2): under 341 ℃, 10 weight % loss; Under 357 ℃, 50 weight % loss.
(D) synthesize 1,1,2,3,3,3-hexafluoropropanesulacidc acidc sodium (HFPS-Na)
To 1 gallon
Figure GPA00001039864800112
Add in the C reaction vessel sodium sulphite anhydrous 99.3 (25g, 0.20mol), sodium bisulfite (73g, 0.70mol) and the solution of deionized water (400mL).The pH of this solution is 5.7.Container is cooled to 4 ℃, empties to 0.08MPa, add then R 1216 (HFP, 120g, 0.8mol, 0.43MPa).Under agitation container is heated to 120 ℃, and under this temperature, keeps 3hr.Pressure rises to the highest 1.83MPa, reduces to 0.27MPa then in 30 minutes.When finishing, with the container cooling, and with remaining HFP emptying, and use the nitrogen purging reactor.The pH that final solution has is 7.3.
Vacuum removes water on rotatory evaporator, obtains wet solid.Then described solid is placed vacuum oven (0.02MPa, 140 ℃, 48hr) in, obtain the white solid that 219g comprises about 1 weight % water.The Theoretical Mass of all solids is 217g.
By with reagent grade acetone extraction, filtration and dry, rough HFPS-Na further can be purified and separate.
19F?NMR(D 2O)δ-74.5(m，3F)；-113.1，-120.4
(ABq，J＝264Hz，2F)；-211.6(dm，1F).
1H?NMR(D 2O)δ5.8(dm，J FH＝43Hz，1H)。
Mp(DSC)126℃。
TGA (air): under 326 ℃, 10 weight % loss; Under 446 ℃, 50 weight % loss.
TGA (N 2): under 322 ℃, 10 weight % loss; Under 449 ℃, 50 weight % loss.
The preparation ionic liquid
(E) two trifluoromethane sulfimide salt of preparation 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone
A) preparation 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone
In 400mL oscillator tube reactor, with ethyl levulinate (18.5g), N, (ESCAT-142 1.0g) mixes for N-dimethyl-ethylenediamine (11.3g) and 5%Pd/C.H at 6.9MPa 2Make to be reflected at and carry out 8hr under 150 ℃ down.
At HP-6890 GC (the Agilent Technologies that is equipped with 25Mx0.25MM ID CP-Wax 58 (FFAP) post; Palo Alto, CA) and HP-5972A GC-MS detector on, come analytical reaction thing and product by vapor-phase chromatography.By adding methoxy ethyl ether, obtain the GC yield as interior mark.The transformation efficiency of ethyl levulinate is 99.7%, and the selectivity of product of 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone is 98.6%.
B) salt compounded of iodine of preparation 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone
For carrying out quaterisation, 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone (1.7g) that purifying is crossed is put in the 5g anhydrous acetonitrile, and added the 1.69g propyl iodide.Under nitrogen atmosphere, this mixture backflow is spent the night; Illustrate by TLC and to react completely, obtain the salt compounded of iodine of quaternary ammonium compound.Vacuum removes acetonitrile then.
C) prepare 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methyl by anionresin Two trifluoromethane sulfimide salt of pyrrolidin-2-one
For carrying out anion exchange reaction, the salt compounded of iodine (1g) for preparing in step (b) quaterisation is joined in the water (5g), add ethanol (5g) then.The two trifluoromethane sulfimides that add stoichiometry, and with mixture stir about 24 hours under nitrogen.Form orange red separating layer in the bottom, its water is washed fast; The upper strata decantation is come out.Salmon liquid was placed 48 hours, to obtain ionic liquid (two trifluoromethane sulfimide salt of 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone) under 100 ℃ and vacuum in baking oven.Followingly study ion liquid stability: use Universal V3.9A TA instrument analyser (TA Instruments by thermogravimetric analysis, Inc., Newcastle DE), is heated to 800 ℃ with the speed of 10 ℃ of per minutes with ionic liquid (79mg); The result confirms, ionic liquid height under to about 300 ℃ be decompose stable.
(F) six of preparation 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone Fluorophosphate
A) the bromine salt of preparation 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone
For carrying out quaterisation, 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone (1g) that synthetic purifying among the embodiment 1 is crossed is put in the 5g anhydrous acetonitrile, and added the 0.71g1-N-PROPYLE BROMIDE.Under nitrogen atmosphere, this mixture backflow is spent the night; Illustrate by TLC and to react completely, obtain the bromine salt of quaternary ammonium compound.Vacuum removes acetonitrile then.
B) prepare 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methyl by anionresin The hexafluorophosphate of pyrrolidin-2-one
For carrying out anion exchange reaction, the bromine salt (0.5g) for preparing in embodiment 2 (a) quaterisation is joined in the water (5g), add ethanol (5g) then.Add two hexafluorophosphates (Sigma-Aldrich) of stoichiometry, add other 2mL water then, with mixture stir about 24 hours under nitrogen.Form separating layer in the bottom, its water is washed fast; The described upper strata of decantation.Then remaining liq was placed 48 hours in baking oven under 100 ℃ and vacuum, to obtain ionic liquid; Obtain the 0.6g ionic liquid.
(G) bromine of preparation 1-(2-N, N, N-dimethyl amyl group amino-ethyl)-5-methylpyrrolidin-2-ketone Salt
A) the bromine salt of preparation 1-(2-N, N, N-dimethyl amyl group amino-ethyl)-5-methylpyrrolidin-2-ketone
For carrying out quaterisation, 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone (1g) that synthetic purifying among the embodiment 1 (a) is crossed is put in the 5g anhydrous acetonitrile, and added the 1.51g1-bromo pentane silane.Under nitrogen atmosphere, this mixture backflow is spent the night; Illustrate by TLC and to react completely, obtain the bromine salt of quaternary ammonium compound.Vacuum removes acetonitrile then, obtains ionic liquid.
B) trifluoro of preparation 1-(2-N, N, N-dimethyl amyl group amino-ethyl)-5-methylpyrrolidin-2-ketone Metilsulfate
For carrying out quaterisation, will derive from 1-(2-N, N-dimethylaminoethyl)-5-methylpyrrolidin-2-ketone (13.5g) that the purifying of step (a) crosses and put in the 20g anhydrous acetonitrile, and add the 10g1-bromo pentane silane.Mixture was heated 4 hours down at 60 ℃.Then trifluoromethanesulfonic acid potassium is joined (the 30mL acetonitrile solution of 9.5g trifluoromethanesulfonic acid potassium) in the acetonitrile.Mixture was stirred 4 hours down at 60 ℃, at room temperature spend the night then.Potassium Bromide is precipitated out.Mixture is filtered, and the solid that will not contain Potassium Bromide is positioned under the vacuum, to remove solvent.With the mixture drying, obtain fluoroform sulphonate, as ion liquid negatively charged ion.Product is confirmed by NMR.The ultimate capacity of ionic liquid (trifluoromethyl sulfonic acid of 1-(2-N, N, N-dimethyl amyl group amino-ethyl)-5-methylpyrrolidin-2-ketone) is 13g.
Embodiment 1: propyl carbinol is to the conversion of dibutyl ether
With 1-butanols (30g), 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2,2-tetrafluoro esilate (5g) and 1,1,2,2-tetrafluoro ethyl sulfonic acid (0.6g) is put in the 200mL oscillator tube.Under pressure and vibration, described pipe was heated 6 hours down at 180 ℃.Then container is cooled to room temperature, and relief pressure.Before heating, component exists with single liquid form.After component reaction and the cooling, described liquid becomes 2 phase systems.Top layer estimates mainly to comprise dibutyl ether and mutually less than 10% 1-butanols.Bottom estimates to comprise 1,1,2 mutually, 2-tetrafluoro ethyl sulfonic acid, 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2,2-tetrafluoro esilate and water.As measured by NMR, the transformation efficiency of 1-butanols is estimated as about 90%.Estimate that two liquid phases are completely different, and several minutes (＜separate in 5min).
Embodiment 2: propyl carbinol is to the conversion of dibutyl ether
With 1-butanols (60g), 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2,2-tetrafluoro esilate (10g) and 1,1,2,2-tetrafluoro ethyl sulfonic acid (1.0g) is put in the 200mL oscillator tube.Under pressure and vibration, described pipe was heated 6 hours down at 180 ℃.Before heating, component exists with single liquid form.After component reaction and the cooling, described liquid becomes 2 phase systems.Top layer is estimated to comprise greater than 75% dibutyl ether with less than 25% 1-butanols mutually, but and does not comprise the ionic liquid or the catalyzer of measuring vol.Bottom shows mutually and comprises 1,1,2,2-tetrafluoro ethyl sulfonic acid, 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2, the 1-butanols of 2-tetrafluoro esilate, water and about 10 weight %, this weight % are the combined wt with respect to ionic liquid, acid catalyst, water and 1-butanols.The transformation efficiency of 1-butanols is estimated as about 90%.Estimate that two liquid phases are completely different, and several minutes (＜separate in 5min).

Claims (16)

1. be used for preparing at reaction mixture the method for dialkyl ether, described method comprises that (a) makes at least a C at least a in the presence of ion liquid 4-C 8Straight chain alcohol contacts with at least a homogeneous acid catalyst, forming the dialkyl ether phase that (i) comprises the described reaction mixture of dialkyl ether, with the ionic liquid of (ii) described reaction mixture mutually; And (b) dialkyl ether of the described reaction mixture ionic liquid with described reaction mixture is separated, to reclaim the dialkyl ether product; Wherein ionic liquid is represented by the following formula structure:
Figure FPA00001039864700011
Wherein:
In positively charged ion, Z is-(CH 2) n-, wherein n is 2 to 12 integer; And R 2, R 3And R 4Be selected from independently of one another H ,-CH 3,-CH 2CH 3, and C 3-C 6The straight or branched univalent alkyl; And
A -Be negatively charged ion, described negatively charged ion is selected from [CH 3OSO 3] -, [C 2H 5OSO 3] -, [CF 3SO 3] -, [HCF 2CF 2SO 3] -, [CF 3HFCCF 2SO 3] -, [HCClFCF 2SO 3] -, [(CF 3SO 2) 2N] -, [(CF 3CF 2SO 2) 2N] -, [CF 3OCFHCF 2SO 3] -, [CF 3CF 2OCFHCF 2SO 3] -, [CF 3CFHOCF 2CF 2SO 3] -, [CF 2HCF 2OCF 2CF 2SO 3] -, [CF 2ICF 2OCF 2CF 2SO 3] -, [CF 3CF 2OCF 2CF 2SO 3] -, [(CF 2HCF 2SO 2) 2N] -, and [(CF 3CFHCF 2SO 2) 2N] -
2. the process of claim 1 wherein that homogeneous acid catalyst is pKa less than about 4 homogeneous acid catalyst.
3. the process of claim 1 wherein that described reaction mixture comprises ionic liquid, described ion liquid content is with respect to C contained in the described reaction mixture 4-C 8The weight of alcohol is about 0.1% or bigger by weight, but is about 25% or lower.
4. the process of claim 1 wherein that homogeneous acid catalyst is selected from mineral acid, organic sulfonic acid, heteropolyacid, fluoro-alkyl sulfonic acid, metal sulfonate, metal trifluoroacetate acetate, their mixture and their combination.
5. the method for claim 1, wherein homogeneous acid catalyst is selected from sulfuric acid, fluosulfonic acid, phosphorous acid, tosic acid, Phenylsulfonic acid, phospho-wolframic acid, phospho-molybdic acid, trifluoromethanesulfonic acid, nine fluorine fourth sulfonic acid, 1,1,2,2-tetrafluoro ethyl sulfonic acid, 1,1,2,3,3,3-hexafluoropropanesulacidc acidc, Bismuth triflate, trifluoromethanesulfonic acid yttrium, Ytterbiumtriflate, trifluoromethanesulfonic acid neodymium, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid scandium and trifluoromethanesulfonic acid zirconium.
6. the process of claim 1 wherein that described reaction mixture comprises catalyzer, the content of described catalyzer is with respect to C contained in the described reaction mixture 4-C 8The weight of alcohol is about 0.1% or bigger by weight, but is about 20% or lower.
7. the process of claim 1 wherein described C 4-C 8Straight chain alcohol is selected from propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol and n-Octanol.
8. the process of claim 1 wherein described C 4-C 8Straight chain alcohol is a propyl carbinol, and described dialkyl ether is a dibutyl ether.
9. the method for claim 1, described method is implemented under inert atmosphere.
10. the process of claim 1 wherein that described dialkyl ether product is in vapor phase.
11. the process of claim 1 wherein that described ionic liquid comprises relict catalyst mutually.
12. the process of claim 1 wherein described isolated ionic liquid is recycled in the described reaction mixture mutually.
13. the process of claim 1 wherein water is removed mutually from described isolated ionic liquid.
14. the process of claim 1 wherein described C 4-C 8Straight chain alcohol is a propyl carbinol, wherein forms described reaction mixture and takes place to the pressure of about 20.7MPa in about 50 ℃ of extremely about 300 ℃ temperature and about 0.1MPa.
15. the process of claim 1 wherein described C 4-C 8Straight chain alcohol is a propyl carbinol, wherein form described reaction mixture and take place to the pressure of about 20.7MPa in about 50 ℃ of extremely about 300 ℃ temperature and about 0.1MPa, and ionic liquid is 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2,2-tetrafluoro esilate.
16. the process of claim 1 wherein described C 4-C 8Straight chain alcohol is a propyl carbinol, wherein forms described reaction mixture and takes place to the pressure of about 20.7MPa in about 50 ℃ of extremely about 300 ℃ temperature and about 0.1MPa, and wherein ionic liquid is 1-(2-N, N, N-dimethyl propyl amino-ethyl)-5-methylpyrrolidin-2-ketone 1,1,2,2, the tetrafluoro esilate, and homogeneous acid catalyst is 1,1,2,2-tetrafluoro ethyl sulfonic acid.
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